Method for production of isocyanatosilanes
View Patent ↗A process is provided for the production of isocyanatosilane from silylorganocarbamate by neutralizing the basic catalyst with an acid to provide an inert metal halide salt, and subjecting the reaction mixture to cracking reaction conditions to obtain isocyanatosilane.
1. A process for preparing an isocyanatosilane which comprises:
a) providing a mixture of silyorganocarbamate and metal alkoxide catalyst employed in obtaining the silylorganocarbamate;
b) neutralizing the metal alkoxide compound of said mixture with halogen-containing neutralizing agent to provide a mixture of silylorganocarbamate and metal salt; and
c) subjecting the mixture of silylorganocarbamate and metal salt to cracking conditions to provide isocyanatosilane.
2. The process of claim 1 , wherein the silylorganocarbamate is of the general formula
R x (R 1 O) 3-x SiR 2 NHCO 2 R
wherein x is an integer having a value of 0, 1, 2, or 3, R represents an alkyl group or halogenated alkyl group of 1 to 12 carbon atoms, a cycloalkyl group or halogenated cycloalkyl group of 5 to 8 carbons, an aryl group of 6 to 14 carbons or an alkaryl or aralkyl group of 7 to 15 carbons, R 1 is separately R or a silyl R 3 Si, or a siloxy group R 3 Si(OSiR 2 ) m wherein m is an integer having a value of 1 to 4, or when x is 0 or 1 two R 1 groups taken together may form a divalent siloxy group R 2 (OSiR 2 ) n wherein n is an integer having a value of 3, 4, or 5 forming a cyclic silxane with the silicon atom bearing the carbamatosilane group, R 2 represents a linear or branched divalent saturated or unsaturated hydrocarbon group of 1 to 20 carbons attached to silicon by a silicon-carbon bond, and wherein R, R 1 and R 2 optionally may contain heteroatom functional groups such as ether, thioether, sulfone, ketone, ester, amide, nitrile, or halogen.
3. The process of claim 1 , wherein the isocyanatosilane is of the general formula
R x (R 1 O) 3-x SiR 2 NCO
wherein x is an integer having a value of 0, 1, 2, or 3, R separately represents an alkyl group or halogenated alkyl group of 1 to 12 carbon atoms, a cycloalkyl group or halogenated cycloalkyl group of 5 to 8 carbons, an aryl group of 6 to 14 carbons or an alkaryl or aralkyl group of 7 to 15 carbons, R 1 is separately R or a silyl R 3 Si—, or a siloxy group R 3 Si(OSiR 2 ) m , wherein m is an integer having a value of 1 to 4, or when x is 0 or 1 two R 1 groups taken together may form a divalent siloxy group R 2 (OSiR 2 ) n , wherein n is an integer having a value of 3, 4, or 5 forming a cyclic silxane with the silicon atom bearing the carbamatosilane group, R 2 represents a linear or branched divalent saturated or unsaturated hydrocarbon group of 1 to 20 carbons attached to silicon by a silicon-carbon bond, and wherein R, R 1 and R 2 optionally may contain heteroatom functional groups such as ether, thioether, sulfone, ketone, ester, amide, nitrile, or halogen.
4. The process of claim 2 , wherein the silylorganocarbamate is at least one of methyl N-3-(trimethoxysilyl)-propylcarbamate, ethyl N-3-(trimethoxysilyl) propylcarbamate, methyl N-3-(triethoxysilyl)propylcarbamate, methyl N-3-(methyldimethoxysilyl)-propylcarbamate, methyl N-3-(dimethylmethoxysilyl)-propylcarbamate, methyl N-3-(triethoxysilyl) propylcarbamate, ethyl N-3-(triethoxysilyl)-propylcarbamate, methyl N-3-(methoxydiethoxysilyl)propylcarbamate, methyl N-3-(trimethoxysilyl) butylcarbamate and methyl N-3-(triethoxysilyl)-butylcarbamate, the isocyanatosilane is at least one of 3-isocyanato propyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, isocyanatobutyltrimethoxysilane, isocyanatobutylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, isocyanatopropylethyldiethoxysilane, isocyanatopropyldimethylmethoxysilane, isocyanatopropylmethoxydiethoxysilane, isocyanatobutyltriethoxysilane and isocyanatopropylphenylmethylmethoxysilane and the silyisocyanurate is at least one of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, 1,3,5tris(methyldimethoxysilylpropyl)isocyanurate, 1,3,5-tris(trimethoxysilylbutyl) isocyanurate, 1,3,5-tris(methyldimethoxysilylbutyl)isocyanurate, 1,3,5-tris(triethoxysilylpropyl)isocyanurate and 1,3,5-tris(phenylmethylmethoxysilylpropyl)isocyanurate.
5. The process of claim 1 , wherein the halogen-containing neutralizing agent is an acyl halide.
6. The process of claim 1 , wherein the halogen-containing neutralizing agent is selected from the group consisting of akyl halides, aryl halides, ammonium halides, carboxylic acid halides, and mixture thereof.
7. The process of claim 6 , wherein the halogen-containing neutralizing agent is selected from the group consisting of acetyl chloride, ammonium chloride, propionyl chloride, butyryl chloride, dimethyl ammonium chloride, diethylammonium chloride and mixtures thereof.
8. The process of claim 1 , wherein the halogen-containing neutralizing agent is selected from the group consisting of chlorosilanes, phosphrous chlorides, and mixtures thereof.
9. The process of claim 1 , wherein the resulting amine is stripped from the reaction mixture prior to cracking.
10. The process of claim 1 , wherein the halogen-containing neutralizing agent is based on equivalent weights of the contained alkoxide of the metal alkoxide catalyst.
11. The process of claim 10 , wherein the amount of halogen-containing neutralizing agent is from about 0.75 equivalents to about 2 equivalents with respect to the contained alkoxide of the metal alkoxide catalyst.
12. The process of claim 11 , wherein the amount of halogen-containing neutralizing agent is from about 1 to about 1.5 equivalents with respect to the contained alkoxide of the metal alkoxide catalyst.
13. The process of claim 1 , wherein neutralization is carried out to a pH of about 3 to about 10 prior to cracking the carbamatosilane.
14. The process of claim 13 , wherein neutralization is carried out to a pH of about 4 to about 7 prior to cracking conditions to provide isocyanatosilane.
15. The process of claim 14 , wherein an acid is added in addition to the halogen-containing neutralizing agent.
16. The process of claim 15 , wherein the acid is selected from the group consisting of polyphosphoric acid, superphosphoric acid, and hydrochloric acid.
17. The process of claim 15 , wherein the acid is a carboxylic acid.
18. The process of claim 15 , wherein the acid is acetic acid.
19. The process of claim 1 , further comprising removal of residual solid material prior to cracking conditions to provide isocyanatosilane.
20. The process of claim 5 , wherein the halogen-containing neutralizing agent is dissolved in suitable a solvent.
21. The process of claim 20 , wherein the solvent is selected from the group consisting of alcohols, aromatic solvents, ether solvents, and mixtures thereof.
22. The process of claim 1 , wherein the purity of the isocyanatosilane is greater than isocyanatosilane obtained when metal alkoxide catalyst is not neutralized with said halogen-containing neutralizing agent.
23. The process of claim 7 , wherein the neutralizing agent is propionyl chloride.
24. The process of claim 8 , wherein the neutralizing agent is selected from the group consisting of methyltrichlorosilane, dichlorodimethylsilane, chlorotrimethylsilane, propyltrichlorosilane, phosphrous oxychloride, phosphorous trichloride, methylchloride benzylchloride, and mixtures thereof.
25. The process of claim 21 , wherein the alcohol solvent is selected from the group consisting of methanol, ethanol, and mixtures thereof.
26. The process of claim 21 , wherein the aromatic solvent is selected from the group consisting of toluene, xylene, and mixtures thereof.
27. The process of claim 21 , wherein the ether solvent is selected from the group consisting of diethylether, tetrahydrofuran, diisopropylether, 1,4-dioxane, diglyme and triglyme, and mixtures thereof.
28. The process of claim 21 , wherein the ester solvent is selected from methyl acetate, ethyl acetate, and mixtures thereof.
29. The process of claim 21 , wherein the chlorinated hydrocarbon solvent is selected from dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chloroform, chlorobenzene, dichlorobenzene and mixtures thereof.
30. The process of claim 21 , wherein the nitrile solvent is acetonitrile, propionitrile, and mixtures thereof.
31. The process of claim 1 , wherein the metal alkoxide catalyst is selected from the group consisting of sodium methoxide, sodium ethoxide, calcium methoxide, calcium ethoxide, sodium propoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium t-butoxide, lithium methoxide, lithium ethoxide, lithium propoxide, and lithium t-butoxide, and mixture thereof.